Process for coating particulate adhesive

ABSTRACT

Processes are provided for applying flowable, particulate, powdered, curable adhesive to a substrate (e.g., a metallic honeycomb structure).

United States Patent [1 1 McKown Jan. 8, 1974 PROCESS FOR COATING PARTICULATE ADHESIVE [75] Inventor: Alan G. McKown, St. Paul, Minn.

[73] Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.

[22} Filed: Oct. 20, 1971 [21] App1.No.: 191,104

Related U.S. Application Data [62] Division of Ser. No. 768,675, Oct. 18, 1968, Pat. No.

260/47 EC, 47 EN; 117/17,21, 161 UT, 161 UZ, 161 ZB, DIG. 6

[56] References Cited UNITED STATES PATENTS 4/1962 Nagel 117/D1G. 6

3,513,012 5/1970 Point 117/17 3,598,626 8/1971 Probst et a1 117/17 3,580,218 5/1971 Grundschober et a1. 117/17 2,962,403 10/1960 Jones 154/459 3,655,818 4/1972 McKown... 117/17 2,879,252 3/1959 Been 260/837 2,947,338 8/1960 Reid 260/837 3,100,160 8/1963 Korpman 260/837 3,208,980 9/1965 Gruver 260/837 3,219,515 11/1965 Rice 260/837 3,312,754 4/1967 Marks 260/837 3,324,198 6/1967 Gruver 260/837 2,713,569 7/1955 Greenlee 260/837 3,386,955 6/1968 Nawakowski: 260/47 FOREIGN PATENTS OR APPUCATIONS 999,383 7/1965 Great Britain 2611/47 Primary Examiner-Wi1liam D. Martin Assistant Examiner-M. Sofocleous Alt0rney-A1exander, Se11, Steldt and Delahunt [57] ABSTRACT Processes are provided for applying flowable, particulate, powdered, curable adhesive to a substrate (e.g., a metallic honeycomb structure).

3 Claims, 4 Drawing Figures PROCESS FOR COATXNG PARTICULATE ADHESIVE This application is a division of parent application Ser. No. 768,675, filed Oct. I8, 1968, now US. Pat.

This invention relates to structural adhesives; more particularly it relates to one part epoxy based structural adhesives in fiowable, particulate form especially adapted for adhering metal sheeting to itself and to honeycomb cores such as are employed in aircraft wing assemblies.

From a historical viewpoint, bonding of an airframe is a recent development. The first production usage of a bonded structure was in World War II bombers. The upsurge of commercial aviation in the post-war period started the trend away from riveted assemblies towards a bonded assembly. The reasons involved were numerous but included cleaner air foil surfaces, improved fatigue strength, and a greater strength to weight ratio through the use of honeycomb construction.

Initially, bonding was confined to control surface area and empennage but as improvements in adhesives were made, the use of adhesives expanded until today it includes a large percentage of the aircraft including wings, rotor blades and fuselage.

The development of film adhesives was a prime factor for this increase in usage as it offered adhesives in 100 percent solids form and permitted application of a controlled amount of adhesive. Other adhesives available were solvent solutions where drying was a major difficulty or 100 percent solids pastes which at least prior to the advent of films did not possess the fine balance of properties required for a structural adhesive.

Adhesives in paste form are even less desirable due in part to their tackiness at the time of application making precise positioning of the bonded elements difficult, difficulty in controlling the amount and location of the adhesive, and the further fact that solvents are required to remove the adhesive from unwanted areas. Liquid solvent containing structural adhesives also lacked suit-- ability due to inability to localize application, the need for solvent removal with its attendant fire and toxicity hazards, and, as with the pastes, the tackiness of the adhesive at the time of application.

With the advent of the large jet aircraft the amount of bonded area per plane and the total number of planes anticipated will far outstrip the production facilities and work force available. It is not considered economically sound to merely increase floor space and hire more labor. For the above reasons, the presently available adhesives, both in terms of composition and form, do not lend themselves to the automated techniques which must be employed to meet this expanding demand.

To achieve a structural adhesive amendable to high production techniques and yet fulfill the stringent requirements of structural adhesives for aerospace environments is the primary object of this invention. These requirements are particularly formidable, calling for an adhesive which exhibits excellent strength properties over a wide temperature range which in turn depends on attainment of a delicate balance of such properties as adhesion, toughness, and tensile strength. The following table indicates the kind and value of properties over a wide temperature range desired in the bonds within such laminate structural members as are found in aircraft:

l. The free ends of strips of 1 inch wide, 4 inches long, 20 mil 2024 T3 clad aluminum alloy sheeting, bonded together at their other ends with 0.08 pound/square inch weight bonding film (used in all the tests) in a /2 inch overlapping joint, are pulled in opposite directions along their longitudinal axes.

2. The adjacent ends of 1 inch wide, 8 inches long strips of 20 mil 2024 T3 clad aluminum allow sheeting adhered together over most of their length are bent apart at right angles and e are pulled in opposite directions. E

3. A free end of a 3 inches wide, 10 inches long, 20 mil 2024 T3 clad aluminum alloy sheeting is pulled from the '/z inch thick, A inch cell honeycomb core of4 mil 3003 aluminum alloy foil to which it is bonded by wrapping the sheeting around a 4-inch diameter roller riding on the surface of the sheeting.

4. Three inches wide, 8 inches long laminates of the described honeycomb core with 64 mil skins of 2024 T3 clad aluminum alloy sheeting are supported by supports spaced 6 inches apart. A 1000 pound weight at 75 F. and an 800 pound weight at 180 F. are loaded midway between the supports. fter hours the deformation of the center of thebeamis measured.

However, even with films various hand lay-up operations are required in making a bonded assembly including removing a protective liner, positioning the film, removing a second protective liner, making cutouts in desired areas, and finally closing the bond. ln addition to involving undue amounts of time, film adhesives suffered from other drawbacks including waste in material from cutting operations, difficulty in applying to contoured surfaces, inability to provide adjustments in thickness, and limitations in compensating for mismatch of parts.

The achievement of such properties when bonding to honeycomb requires an adhesive that not only exhibits strength properties in the' cured state, but that also, when first heated, has flow and other characteristics necessary to wet and form a fillet. along the contacted edge portion of the honeycomb. Moreover, the presence of aluminum as the substrate in the majority of aerospace structures to be bonded necessitates imposition of a limitation in the curing temperature of the adhesive in order to avoid reduction in corrosion and fatigue resistance of the aluminum. As a consequence,

curing temperatures not exceeding about 250 F. are highly desirable and in some cases necessary.

The present invention provides a structural adhesive possessing the above stated properties as well as being amenable to automated techniques of application, such structural adhesive being a flowable particulate comprising at least one heat curable epoxy resin having on the average more than one 1,2 epoxy group per molecule, at least one copolymer of butadiene and acrylonitrile, and a curing system for said epoxy resin comprising at least one room temperature stable, nitrogen containing compound decomposable to form at least one amine having at least one active hydrogen atom.

Adhesives of the above composition and particulate form may be applied to various automatic means including rollers, electrostatic spray equipment, fluidized beds, and vibrating beds. In the completely uncured state, the adhesive is a flowable particulate which can be readily removed from undesired areas by means of a vacuum tool. Upon subjection to temperatures above about 120 F. and below the cure temperature, generally about 230-250 F., the adhesive enters an agglomerated, fused state in which it adheres strongly to the substrate to which it is applied and yet is not tacky or sticky enough to cause individually treated substrates to stick together during storage or shipment. Moreover, in this state, the treated parts can be manipulated into the bonding position without the need for careful precautions to insure precise initial matching. The adhesive can remain in this fused adherable, non-tacky, curable state for periods of up to about 45 days at temperatures less than about 90 F.

Because of this stability in an adherable state, it is now possible for the manufacturer of the basic structural elements, e.g. the manufacturer of panels and honeycomb structures, to pre-coat such elements with the adhesive, selectively remove adhesive from undesired areas, heat the adhesive to a fused, adhering state, and ship the resulting product to the ultimate fabricator such as the airplane manufacturer. Thus, the adhesive of this invention provides the opportunity for a form of marketing of structural units hitherto impossible with previous structural adhesives, giving the ultimate manufacturer the option of concentrating on the final assembling techniques to which it is best suited.

Epoxy resins suitable in the practice of this invention are thermosettable polyethers having on the average m e thanons LZs xyaro p r2 1 @ecule nql atn the diglycidyl ethers of polyhydric phenols, glycidyl ethers of novolac resins, glycidyl ethers of aliphatic polyols, and glycidyl ethers containing nitrogen. Preferred diglycidyl ethers of polyhydric phenols include the condensation product of epichlorohydrin and Bisphenol A, especially those with an epoxy equivalent between about 550 and about 700 and a softening point between about 75 C. and 85 C. Exemplary commercially available Bisphenol A type epoxy resins are sold under the trade designations Epon 1002 and DER 662. The glycidyl ethers of novolac resins are characterized by phenyl groups linked by methylene bridges with epoxy groups pendant to the phenyl groups, commercially available resins being sold under the trade designation DEN-438 and ECN 12 80. Commercially available glycidyl ethers of aliphatic polyols include those having the trade designations ERL-4201 and ER- L-4289. A commercially available glycidyl ether containing nitrogen is ERL 0510.

The epoxy resin may be solid or liquid so long as the overall adhesive composition constitutes a grindable mass, at least in the presence of dry ice, which will provide a powdered adhesive at room temperature. Some agglomeration of adhesive may occur at room temperature but the adhesive should be capable of being broken up into matter having particulate character. It is preferred that at least some novolac epoxy resin be present to provide high temperature strength to the adhesive. Weight ratios of novolac epoxy to non-novolac epoxy resin of from 1:7 to 3:1 are suitable, with a major portion of novolac epoxy resin being preferred. If a liquid epoxy resin is employed, particularly a glycidyl ether of an aliphatic polyol or phenol, it should be combined with a major portion of solid epoxy resin, preferably at least as much as percent by weight of the combined epoxy resin weight.

The nitrile rubber copolymers of butadiene and acrylonitrile serve as modifiers for the epoxy resins. Preferably, the nitrile rubber contains a small percentage of carboxyl groups either terminally located or distributed throughout the polymer chain or both. Nitrile rubbers derived from 18-46 percent acrylonitrile, 5582 percent butadiene, and 0-15 percent of a carboxylic acid represent typical formulations suitable in the practice of this invention. Commercially available nitrile rubbers include those sold under the trade designations Hycar 1072, Tylac 221A, Tylac 21 1A, Chemigum 550, and Hycar 1042 (non-carboxylated). The preference for carboxylated nitrile rubbers appears to be due to the reaction which occurs between the carboxyl groups and the epoxy groups which are activated during the curing or crosslinking reaction, thereby making the nitrile rubber an integral part of the cured system. While this integration is highly preferred, suitable adhesives have been provided without carboxylated nitrile rubbers.

The curing system for the epoxy resin includes at least one room temperature stable, nitrogen containing compounds decomposable to provide at least one active hydrogen containing amine. Decomposition generally occurs at a temperature between F. and 250 F. to provide curing in that temperature range generally within a period of one hour. For certain applications, especially for bonding aluminum substrates in aerospace structures, curing temperatures not exceeding 250 F. are desired. For other substrates, curing systems providing a cure at about 350 F. is suitable. Exemplary decomposable curing agents include monoand poly-ureas, thioureas, and hydrazines, illustrative of which are the following:

3-phenyl-1,1-dimethyl urea;

3-p-chlorophenyl l,l-dimethyl urea;

3-p-anisyll l -dimethyl urea;

3-p-nitrophenyll l -dimethyl urea;

3-phenyl-l 1 -cyclopentamethylene urea;

3-phenyl-1 ,1 -cyclohexamethylene urea;

N-(3,4-dichlorophenyl)-N', N'-dimethyl urea;

3-phenyll 1 -dibutyl urea;

3-phenyll -benzyl- 1 -methyl urea;

trimethylurea;

3-phenyl-1,1-dimethylene urea;

3-cyclohexyl-1,l-dimethyl urea;

2,4-bis (N,N-dimethyl carbamide) toluene;

N,N'-dimethyl-l,3-propane diamine dicarboxanilide;

1,3-dicyclohexyl urea;

dimethyl urea, 3-p-cblorophenyl-l,1-dimethyl urea, and 3-p-nitropheny1-l ,l-dimethyl urea.

The active hydrogen containing amine decomposition product functions as a curing agent for the epoxy resin via an epoxy to epoxy crosslinking reaction. Whereas curing can be effectuated by the presence of such decomposition products alone, it has been found preferable to include certain curing agents such as dicyandiamide and isophthalyldihydrazide which alone provide epoxy curing at about 325 F. It has been found that such compounds in combination with the heat decomposable nitrogen containing compounds, such as 3-(p-ch1orophenyl)-1,1 dimethylurea and the like, provide a curative effect at temperatures as low as 190 F. For some reason not readily explainable the presence of these elevated temperature curing agents such as dicyandiamide and isophthalyldihydrazide contribute to the improvement of the physical properties of the cured system.

In addition to the room temperature stable, elevated temperature decomposable nitrogen containing compound, the curing system may contain (2) a hydroxyl containing organic compound and (3) an organo lead or mercury compound. Such a three-component curing system is disclosed in US. application Ser. No. 644,797 assigned to the common assignee. This curing system further reduces the cure temperature of the epoxy resin from about 250 F. to a temperature generally below 200 F.

The hydroxyl containing compound may be an aliphatic, alicyclic, or aromatic alcohol, carboxylic acid, hydroxy acid, or mixture thereof. Such compound may contain one or a plurality of hydroxy or carboxyl groups. Aliphatic polyhydroxy compounds are preferred, especially ethylene glycol and glyerol. Representative hydroxyl containing compounds are the fol lowing: ethylene glycol, glycerol, triethylene glycol, bisphenol A, methanol, n-butanol, phenol, o-cresol, mcresol, p-cresol, resorcinol, o-bromophenol, n-hexanol, trichloracetic acid, and mixtures thereof.

Exemplary organo-mercury and organo-lead compounds are phenyl mercuric hydroxide, phenyl mercuric acetate, phenyl mercuric stearate, lead octoate, lead linoleate, and lead acetate. The organo-mercury and organo-lead compounds, in combination with the nitrogen containing compound and the above described hydroxyl containing compounds, provide an unexpectedly rapid curing system for epoxy resins.

When employing the three component curing system, a major amount of the nitrogen-containing component and minor amounts of each of the other two components are generally employed. However, this could be reversed so that either of the hydroxyl containing or organo-metallic compound is in the majority. An excess of any of the three ingredients is :not detrimental to the adhesive; it will merely serve as a filler. A suitable composition of the three component cure system is one containing about 0.025 to about 500, preferably about lto about 25, parts of nitrogen-containing compound ei'pr'tof hydroxyl containing compound, and about 0.05 to about 5,000, preferably about 1 to about 250, parts of nitrogen-containing compound per part of organo-metallic compound. Here, as elsewhere in the specification and claims, parts are by weight unless stated to the contrary.

In addition to the foregoing, the adhesive composition of this invention may include fillers and the like. Particularly desirable is a finely divided inorganic oxide such as titanium dioxide which has been found to promote sprayability in electrostatic equipment. Other suitable nq aaa s ase r al i ume d and calcium oxide (CaO). Another highly desirable component for inclusion in the adhesive of this invention is a corrosion inhibitive pigment such as a metal chromate (zinc, cadmium, calcium, strontium, lead, barium); By including a corrosion inhibitor directly into the adhesive, it has been found unnecessary to separately treat the metal surface to be bonded with a corrosion inhibitive primer.

The substrates to be bonded may be treated with adhesion promoting primers such as organosilanes to improve the bond strengths of the adhesive as is well known to the art.

The amount of the various components of the adhesive composition of this invention may vary over rather broad ranges. The nitrile rubber may suitably be present to the extent of from about 6 to about 54 parts by weight per parts by weight of epoxy resin, with a range of 1540 parts by weight being preferred. The novolac epoxy resin may be present to the extent of from about 10 to about 300 parts by weight per hun dred parts by weight of non-novolac epoxy resin with from 30 to 100 parts per 100 parts of non-novolac epoxy resin being preferred. The curing system may suitably be present in an amount of at least 0.15, and preferably at least 0.8, amine hydrogen equivalents per epoxy equivalent. Higher levels of curing agents are not detrimental as they serve merely as fillers, albeit expensive ones. The metal oxide and the corrosion inhibitive pigment may each be present to the extent of from 0 to about 36 parts by weight per 100 parts by weight of epoxy resin.

Spraying, fluidized beds, and vibrating beds represent automated techniques for applying the adhesive of this invention to the substrate to be bonded. Because of the powdery nature of the adhesive, it can be readily removed by vacuum tools where desired. A preferred method comprises contacting a supply of powdered adhesive with a honeycomb core structure which is at a temperature sufficiently high to cause the adhesive to transfer to the core edges (about F.) and yet insufficient to activate the elevated temperature decomposable curing agent, removing the adhesive coated core from the supply and, cooling the core structure such that the adhesive assumes a fused, non-tacky, adhering state.

The supply of powdered adhesive contacted by the heated core may suitably be in the form of a flatbed or coating on a roller. Adhesion of the powder to the roll surface can be maintained by electrostatic forces, vacuum forces, friction such as found in a pile type fabric, or the force of attraction which the roll surface inherently possesses with respect to the powdered adhesive.

The nitrile rubber is banded on a conventional rubber mill after which the epoxy resin and novolac resin, each in powder form, are added to the rubber on the mill and the mixture blended to a homogeneous mass.

A typical honeycomb assembly to be bonded by the In successive order, the titanium dioxide, dicyandiadhesive of this invention is illustrated in FIGS. 14 amide, and 3-p-chlorophenyl l,l-dimethyl urea are wherein: added. During addition of the latter ingredients, the

FIG. 1 illustrates an airplane in which structural rubber mill is cooled with circulating water to prevent members are bonded with the adhesive of this invenheat buildup. After uniform mixing is obtained, the adtion; hesive formulation is promptly removed from the mill FIG. 2 is a cross-sectional view of the wing assembly and refrigerated at 0 F. to prevent any reactions from taken along line 22; occurring. The adhesive is then ground with dry ice in FIG. 3 is a sectional view taken along line 3-3 of a hammer mill to produce aparticle size which will pass FIG. 2; and through a 60 mesh screen. The resulting powdered ad- FIG. 4 is an, enlarged fragmentary view of the bonded hesive may be s tc re d indefinitely at 75 F. V area of the honeycomb core of FIG. 2. The powdered adhesive is then applied to at least one Referring to FIGS. 14, section 1 of a wing assembly of the two elements to be bonded by one of the follow- 3 is shown. The section 1 comprises a doubler portion ing methods: consisting of aluminum panels 5, 7, and 9 bonded by l. Electrostatic Spraying. Employing an electrostatic adhesive layers 11 and 13. The honeycomb core 15 is spray gun such as a Ransburg REP hand gun, the powbonded to the outer aluminum panels or skins 5 and 9 dered adhesive is electrostatically charged while passby means of an adhesive layer 17 and filleting adhesive ing through the gun. The powdered, electrostatically 19 FIGS- 3 and h dh s lay r 17 and charged adhesive issuing from the gun is applied to an letlng adheswe 19 may be of the same or dlfferent electrically grounded metal sheet by electrostatic atpositlons falling w1th1n the scope of the present 1n traction. Excess adhesive is removed by brushing or h hf h y adhesive layer 17 Contains Corrosion suction using a vacuum tool. The adhesive is then fused lhhlbltlve p g e AS pe y Show" I FIGS 3 to the metal surface by heating at 150 F. for 10 minf the fihehhg adheslve Occurs Substantially eXehlutes in an air circulating oven. At this stage, the adhel) along the edges 21 the honeycomb Cells sive is firmly adhered to the surface in a non-tacky, une y the Inna-Cellular P 23 p Core cured state. The parts to be bonded are then assembled [1on5 f p together y means of an expandable and the adhesive cured by subjecting the assemblage to ad hes1ve 25 whlch may be 1n the form of a tape or other a temperature of and a pressure of 50 psi for 60 suitable form. The channel closeout portion 27 1s also minutes in an autoclave Joined to h honeycomb core y means of an expand 2. Fluidized bed. The metal substrate such as a honable eycomb core is preheated to 150 F. and then dipped To further 1llustrate the mventlon, the followmg noninto a fluidized bed of the above adhesive The adhe hmmng examples are Provided m wh1ch pans and sive fuses to the core edges, with the intra-cellular area Percentages are by wglght unless Otherwls? PW EQ- being free of adhesive. The desired assemblage is completed and the adhesive cured as above. 40 3. Powder bed. The metal substrate is preheated to EXAMPLE 1 150 F. and then brought into contact with a pile fabric Matenal Parts by Welght surfaced roller bearing a layer of loosely adhermg pow- Carboxylate d nitrile rubber 321 der. The heat fuses the adhesive particles to the sub- 5533 22 3; strate. Assemblying and curing are accomplished as r10 80 above. Dicyandiamide 31.2 3-p-chlorophenyl l,l-dimethyl urea 20.1 EXAMPLES 2 12 Adhesive compositions l-ll are prepared in accor I 3132113,; dance with Example 1. Each adhesive is tested with 3. Trade designation ECN -l280. the results shown 1n Table Table l Nitrile Epoxy Amine H Sample Epoxy Resin Rubber Curing System Equiv. Equiv 1 Epon 89 ECN 11 Hycar 36 Dicy' 3.5 P-CPDMU 2.25 .191 .178

1002 1280 1072 2 Epon 34.9 ECN 65.1 Hycar 26.5 Dicy 6.9 P-CPDMU 4.48 .384 .351

840 1280 1072 3 Epon 31.5 ECN 68.5 Hycar 27.0 Dicy 7.32 P-CPDMU 4.72 .398 .373

836 1280 1072 4 Epon 73.2 ECN 26.8 Hycar 27.1 Dicy 4.31 P-CPDMU 2.78 .234 .219

1002 I280 1000 28 5 Epon 89 ECN 11 Tylac 36 Dicy 3.5 P-CPDMU 2.25 .191 .178

1002 1280 221A 6 Epon 73.1 ECN 26.9 Hycar 27 Iphy' 6.57 P-CPDMU 2.78 .234 .151

1002 1280 1072 7 Epon 89 ECN 11 Hycar 26.8 Dicy 4.45 MMPD 1.94 .191 .227

1002 1280 1072 8 Epon 80.4 ECN 19.6 Tylac 36 Dicy 3.16 P-CPDMU 2.03 .169 .160

Table 1- Continued Nitrile Epoxy Amine H 3 Sample Epoxy Resin Rubber Curing System Equiv. Equiv 9 Epon 77 DEN 23 Hycar 36.2 Dicy 4.54 P-CPDMU 2.93 1 .251 .231

1002 438 1072 Epon 73.2 ECN 26.8 Hycar 27 Dicy 3.28 PDMU 5.46 .234 .189

1002 1280 1072 11 Epon 89 ERL 11 Hycar 26.9 Dicy 4.44 P-CPDMU 2.86 .240 .225

I. All parts are by weight. 2. Para-chloro phenyl dimethylurea. 3. 1,1"(4-methyl meta phenylene) bis 3,3-dimelhylurea. 4. Phcnyl dimethyl urea. S. Dicyandiamide 6. lsophthalyldihydrizide. m

Table 2 O.L.S. T-PEEL' HONEYCOMB PEEL Sample 67F. 75F. 180F. 250F. 67F. 75F. 180F. 250F. 67F. 75F. 180F.

1 4637 5573 2130 750 10 24 4.5 24 49 19 2 1408 4000 2038 1025 1 ll 4 2.5 3.8 8.7 5.5 3 2282 4012 3205 2348 1.5 13.5 6 S 6.3 8.0 8.0 4 3563 2753 2023 903 3.8 9.2 3 11 6 8 8 5 4440 4936 1750 962 8.0 34 26 5 8.3 30.6 10.4 6 311116 4906 2257 970 5.8 14.2 8 5 12.4 28.3 13.2 7 38211 4661 27511 1292 4.5 24.0 15.8 3.5 8.9 37.2 23.4 8 4086 4170 1590 607 5.11 19.5 17.2 3.5 11.7 17.6 5.9 9 5020 5385 2175 730 19.8 23.0 14.2 2.2 21.2 21.7 4.8 10 3880 4513 1897 755 5.2 9.5 9.2 3.5 6.4 12.7 17.5 11 4721 5613 3072 948 9.0 42 19.2 6.5 16.0 33.1 25.5

8. Overlap sheer strength in pounds/in. 9. Metal to metal peel strength in pounds per inch width. 10. Climbing drum sandwich in inc h pounds per inch width. A r

While the present invention has been particularly described with respect to aluminum substrates employed in aerospace structures, it is to be understood that the adhesive of this invention finds application to a variety of other substrates such as wood, steel, plastics and the like.

What is claimed is:

1. A process for the application of a flowable, particulate, powdered, curable adhesive to a metallic honeycomb structure comprising heating said metallic honeycomb structure to a temperature above room temperature and below the curing temperature of said adhesive, contacting the cellular surface of said heated honeycomb structure with a supply of said adhesive, and removing said honeycomb structure from said supply whereby said adhesive selectively transfers substantially exclusively to the cellular edges of said honeycomb structure where said adhesive assumes a fused, nontacky, curable, adhering state; wherein said curable adhesive comprises:

a. at least one curable epoxy resin having on the average more than one 1,2 epoxy group per molecule,

b. a copolymer derived from 18 percent-46 percent by weight acrylonitrile, percent-82 percent by weight butadiene, and 0 percent-l5 percent by weight of a carboxylic acid said copolymer being present to the extent of from about 6 to about 54 parts by weightper parts by weight of said epoxy resin, and

c. an epoxy curing system present in an amount of at least 0.15 amine hydrogen equivalents per epoxy equivalent comprising at least one room temperature stable urea compound decomposable below 250 F. to provide at least one active hydrogencontaining amine, wherein said adhesive, after a 1 hour cure at 250 F., exhibits an overlap shear value of at least 1,500 p.s.i. in the range of 67 F. to 180 F.

2. A process for the application of a flowable, particulate, curable adhesive to a substrate comprising electrostatically charging said adhesive, spraying said electrostatically charged adhesive on said substrate, and heating said substrate to a temperature sufficiently high to cause said adhesive to adhere to said substrate but not high enough to cause curing of said adhesive; wherein said curable adhesive comprises:

a. at least one curable epoxy resin having on the average more than one 1,2 epoxy group per molecule, b. a copolymer derived from 18 percent-46 percent by weight acrylonitrile, 55 percent-82 percent by weight butadiene, and 0 percent-15 percent by weight of a carboxylic acid, said copolymer being 12 containing amine, wherein said adhesive, after a 1 hour cure at 250 F., exhibits an overlap shear value of at least 1,500 p.s.i. in the range of 67 F. to 180 F,

3. The process of claim 2 wherein said substrate is a metallic honeycomb structure. 

2. A process for the application of a flowable, particulate, curable adhesive to a substrate comprising electrostatically charging said adhesive, spraying said electrostatically charged adhesive on said substrate, and heating said substrate to a temperature sufficiently high to cause said adhesive to adhere to said substrate but not high enough to cause curing of said adhesive; wherein said curable adhesive comprises: a. at least one curable epoxy resin having on the average more than one 1,2 epoxy group per molecule, b. a copolymer derived from 18 percent-46 percent by weight acrylonitrile, 55 percent-82 percent by weight butadiene, and 0 percent-15 percent by weight of a carboxylic acid, said copolymer being present to the extent of from about 6 to about 54 parts by weight per 100 parts by weight of said epoxy resin, and c. an epoxy curing system present in an amount of at least 0.15 amine hydrogen equivalents per epoxy equivalent comprising at least one room temperature stable urea compound decomposable below 250* F. to provide at least one active hydrogen-containing amine, wherein said adhesive, after a 1 hour cure at 250* F., exhibits an overlap shear value of at least 1,500 p.s.i. in the range of -67* F. to 180* F.
 3. The process of claim 2 wherein said substrate is a metallic honeycomb structure. 